Morpholino carbonyl glyoxylonitrile oximino dialkyl carbamates

ABSTRACT

HETEROCYCLIC GLYOXYLONITRILE OXIMINO CARBAMATES ARE USEFUL TO CONTROL PLANT GROWTH, PARTICULARLY THE PRE-EMERGENCE OF UNDESIRABLE GRASSES. THEY MAY BE COMBINED WITH HERBICIDAL CARRIERS AND APPLIED TO THE SOIL, SEEDS, SEEDLINGS, AND TO PLANTS.

United States Patent Int. Cl. C07d 87/44 US. Cl. 260-2472 2 Claims ABSTRACT OF THE DISCLOSURE Heterocyclic glyoxylonitrile oximino carbamates are useful to control plant growth, particularly the pre-emergence of undesirable grasses. They may be combined with herbicidal carriers and applied to the soil, seeds, seedlings, and to plants.

RELATED APPLICATIONS This application is a division of application Ser. No. 598,889, filed Dec. 5, 1966 (now US. Patent 3,843,246). It is a companion of application Ser. No. 817,140 (now US. Patent 3,495,968), filed concurrently herewith, which is directed to aromatic glyoxylonitrile oximino carbamates for such control of plant growth.

This invention relates to new compounds useful in controlling plant growth. It further relates to a method for killing undesired plant life by applying the said compounds thereto or to the seeds thereof. Still further, the invention relates to plant controlling compositions containing a minor amount of the new compound and a major amount of an inert carrier therefor.

The new compounds of the invention are organoglyoxylonitrile oximino carbamates of the formula wherein Ar is an organic radical selected from the group consisting of aromatic, heterocyclic, and combinations of these as parts of the same radical, which radical may have submitted thereon a member of the group consisting of hydrogen, halogen, thiocyanato, N0 C -C alkoxy, C -C haloalkyl, aryl, substituted aryl, aroyl, cyano, C -C alkylmercapto, alkyl sulfonyl, aryl sulfonyl, haloalkyl sulfonyl, C -C carbalkoxy, C -C dialkylamino, amide, C -C alkyl, and C -C cycloalkyl, R and R are selected from the group consisting of hydrogen, C -C alkyl, C -C alkenyl, cycloalkyl, phenyl, and halophenyl, wherein not more than one of R and R is hydrogen, and X is a member of the group consisting of oxygen and sulfur.

It will be understood from the above definition of the generic formula that the organic radical may be free of substitution, or it may have one, two, or more of the named substituents as parts of its nucleus.

Included among the aromatic radicals which form a part of the oximino nucleus are phenyl, naphthyl, indanyl, and other multiple ring radicals containing up to about three rings. The heterocyclic systems contemplated contain a single ring having therein oxygen, sulfur, nitrogen, or combinations thereof. Examples are radicals derived from furan, piperidine, pyridine, morpholine, thiazole, and the like. Included among the systems which contain a combination of aromatic and heterocyclic portions as part of the same radical are quinolinyl, benzothienyl, benzofuranyl, and the like.

3,575,972 Patented Apr. 20, 1971 "ice . As is well known to those familiar with this art, effect1ve control of undesired vegetation governs, to a large degree, yields from food crops. When weeds and other unwanted plants are controlled, one source of competition for the available moisture, nutrients, sunlight, and the like is eliminated. Furthermore, elfective control also increases the efiiciency of maintenance along roadways and railroad tracks, near industrial buildings, along power line rights-of-way, and the like.

The problems associated with effective control of undesired plants in each of the named areas are quite different. For example, when treating crops, or land which is being prepared for crops, the herbicide chosen must be selective in its activity. That is, it must be able to kill weeds and other unwanted plants. but it must be harmless to the food crop plant growing or to be grown in the treated area. When treating certain other areas, however, it may be desirable to kill all plant life. Such will be the case when treating along power line rights-of-way, and a herbicide which is non-selective will be most useful.

Chemical herbicides are classified generally according to the type of activity possessed thereby. A given compound may possess more than one type of activity depending upon its mode of application and the rate at which it is applied. Herbicides are generally classified as selective or non-selective pre-emergents or post-emergents. The former are applied to the soil before the seeds germinate, and to be effective, they must be in intimate contact with the seeds, or with the germinated seedlings. Since weed seeds will germinate closer to the ground than crop seeds, a non-selective pre-emergence herbicide can be effectively used if its penetration is limited to a depth above the crop seeds. This is not always possible, however.

The most effective pre-emergence herbicide, therefore, is the one which is selective in its nature. If the selected compound will kill seed, germinating seed, and seedlings of undesirable plants without harm to the seed, germinating seed, and seedlings of the crop, there is no danger from over-penetration.

Post-emergence herbicides, on the other hand, are applied after the crop and weeds have attained substantial height. Generally speaking, if a compound is found to have post-emergence activity, it will not be selective. This is in keeping with the observation that, as a rule, herbicidally active compounds will not posses selectively as to the type of plant it will attack. It is thus surprising when a group of compounds is found which selectively kills undesirable plants.

Accordingly, it is a broad object of this invention to provide a new class of herbicides which may be used to selectively kill undesired plants, or which may be used as non-selective eradicants. It is a specific object to provide new organoglyoxyonitrile oximino carbonates which may be used as selective or nonselective herbicides. Other objects and advantages of the present invention will become apparent to those skilled in this art from the following detailed description of the invention.

The compounds of the invention may be prepared in one of two ways. In a first method, one part of an organoglyoxylonitrile oximino sodium salt of the formula wherein Ar is as above-defined, is reacted with one part of a carbamyl halide of the formula 1 Hal- 0 (X) N wherein R R and X are as defined earlier and Hal is halogen, so that the overall reaction may be represented by the equation In a second method, a 5 to excess of an appropriate isocyanate or isothiocyanate of the formula CH NCX wherein X is oxygen or sulfur, is reacted with a free oxime of the formula AI(|]=NOH wherein Ar is as already defined. The reaction may be represented by the equation As can be seen, only those compounds wherein one of R and R is hydrogen can be prepared by this second method.

The organoglyoxylonitrile oximino sal-ts (e.g., the so dium salt) can be prepared by the method described by J. T. Thurston and R. L. Shriner in J. Org. Chem. vol. 2, pp. 192493 (1937), in which a cyanide (e.g., benzyl cyanide) is reacted with an appropriate base (e.g., sodium ethoxide) in an alcoholic solvent, followed by addition of butyl nitrite' with preparation of the desired oximino salts.

The free oxime can be prepared by acidifying an aqueous solution of the oximino salt with dilute aqueous hydrochloric acid followed by filtering and drying the solid product.

The carbamate compounds of the present invention are stable and well-defined, and are particularly suited for herbicidal use when employed alone or in combination with inert carriers generally utilized in the herbicide art. The carrier adjuvants may be liquid or solid, depending upon the area to be treated, the type of plant to be controlled, and the kind of equipment available for application. When employing liquid formulations, they may be in the form of true solutions, dispersions, or emulsions. The compositions will contain a minor, herbicidal amount, of compound and a major amount of the carrier therefor.

Solutions, as used herein, means that the compounds of the invention are of molecular size held in true solution by any suitable solvent therefor. It is noted that the inventive compounds are generally water insoluble, thus requiring an Organic solvent when true solutions are desirable or necessary. Acetone, for example, can be used as the solvent. Others will be obvious to those skilled in the art.

The term dispersion covers those liquid phases in which the active ingredient is colloidal in size and which is distributed throughout as particles held in suspension by wetting agents or by soaps. The dispersive medium is usually totally aqueous, but it may contain small quantities of organic solvent, i.e., amounts not suflicient to cause solution of the active member, as well as a small amount of wetting agent.

The wetting agents referred to, in addition to aiding in suspending the toxic particles, are useful as aids in uniformly distributing the active material over the area to be treated, particularly when used as post-emergence herbicides. In other words, the wetting agent helps to prevent build-up of droplets on certain portions of the area, whereupon other portions are left untouched or insufficiently treated by the toxicant, and for this reason a wetting agent may be desirable in most liquid and solid for- 4 mulations. These wetting agents are so well known to the art that is would serve no useful purpose to enumerate them here. As one illustration, Tween-20 (a polyethylene sorbitan monolaurate) is an example of a useful agent which can be used.

Solid formulations contemplated may be bodies of dusts or granules containing herbicidal amounts of the carbamates of this invention. Many solids are known by the art to be useful as herbicidal carriers. Examples of these are kaolin, talc, kieselguhr, diatomaceous earth, pyrophyllite, bentonite, calcium carbonate, powdered cork, wood, walnut shells and peanut shells, fullers earth, tricalciu-m phosphate, and the like.

Dust or granular formulations may be prepared by grinding carrier and chemical together, followed by tumbling for a sufficient time to obtain adequate distribution of chemical. However, a more uniform product can be made if the active ingredient is dissolved in a volatile solvent, such as acetone, prior to admixing with the carrier, added to a tumbling mass of carrier, tumbled until wellmixed, and then dried in any convenient manner. The mass may be dried by applying heat thereto while tumbling or by spreading it into a thin layer and allowing it to dry in the open.

Additionally, the inventive compounds may be applied as aerosols, in which case it is convenient to dissolve them in any suitable solvent and to disperse this solution in dichlorofiuoromethane or other chlorofluoroalkane having a boiling point below room temperature at ambient pressures. It is contemplated that other suitable materials boiling below room temperature will also be useful for this purpose.

The concentration of the chemicals in the compositions disclosed herein may vary over a wide range provided a herbicidal or toxic dosage thereof is placed upon the plant or in its immediate surroundings. Thus, the important consideration is not minimum and maximum concentrations, but the most economical concentration. The inventive herbicides are effective over the range of from about one pound to about 30 pounds of active ingredient per acre treated, and the most suitable ratio of carrier to active ingredient will depend upon the amounts of each needed to ensure even coverage over the acreage treated.

In controlling undesirable plants with the new chemicals as pre-emergents, the toxicant or compositions containing it may be sprayed (if a liquid) or spread (if a solid) over the ground. Thereafter, the material may be left to the natural action of rainfall, or it may be drenched or plowed and disked into the soil. When used as post-emergents, a solid formulation may be dusted onto the plants by the same method used to apply other well known solid herbicidal compositions. When liquid sprays are employed to treat plants, the liquid composition may be sprayed thereon just to the point of liquid run-01f.

Having described the invention in general terms, the following examples of the chemicals of this invention and their use as herbicides are offered. It will be understood that the examples given merely illustrate the invention by way of specific embodiments, and thus are not to be construed as limitations upon it. The invention, with respect to the chemicals themselves and to their use as herbicides, is to be limited only to the extent of the broader definition set forth hereinbefore, the appended claims and reasonable equivalents flowing therefrom. In the examples, parts are parts by weight unless otherwise designated.

EXAMPLE 1 Five parts of p-fiuorophenylglyoxylonitrile oximino sodium salt and about 45 parts of benzene were placed in a suitable reactor equipped with a dropping funnel, a stirrer, and a condenser. Three parts of dimethylcarbamyl chloride was added at room temperature, with stirring, whereupon the reaction mixture was heated to reflux, and held there, with stirring, for three hours. Thereafter, the reaction mixture was cooled to 25 C. and was stirred for an additional 15 hours. The sodium chloride which formed during the reaction was removed by filtration, and the reaction solution was taken to dryness to give 7.5 parts of crude product. A portion of the crude product was recrystallized from hexane, the purified product having 17.59% of nitrogen (theory 17.86% nitrogen), and a melting point of 115-117 C.

EXAMPLE 2 Five parts of p-fiuorophenylglyoxylonitrile oxime, 1.64 parts of methyl isocyanate, about 60 parts of toluene, and

6 three drops of dibutyltin diacetate were charged to a pressure bottle and allowed to stand for 16 hours at C. Four parts of product were isolated. The product was a white solid having the following properties:

M.P. 175184 C. N (calculated) 18.99; N (found) 18.83%. H (calculated) 3.65%; H (found) 3.80.

EXAMPLE 3 In a manner similar to Example 2, the compound was prepared from p-fluorophenylglyoxylonitrile oxime and 3,4-dichlorophenylisocyanate. It was a solid melting at 193.5-195 C., and contained 11.27% N (theory 11.93% N).

' Following substantially the procedures as outlined in Examples 1 and 2 the following compounds were prepared.

Elemental analyses, percent Caleulated Found Compound M.P., O. C H N O H N Example 21: 4 ---o=Noc o)N(cHm sass 10.35 10.40

11: 5 ..C=NOQ(O)NHCH4 170-14 20.68 21.28

CN 0 om-o=noo om om)a 132-134 10.11 18.10

1 1 C=NOC(O)N(CH;)0 05-91 18.17 10.14

I (IN 8 ..-o=Noc o)N crn)1 -113 02.32 5.07 02.21 5.82

: (IN 9 CH;C=NOC(O)N(CH=)4 98100.5 11.13 17.40

ON 10 um-o=noo omwmn 109415 10.70 15.44

311 11 C=NOC(O)N(CH;)1 005-93 4.01 ..405

(|)N 12 o1 c=noc omnon om)i -140 54.24 4.55 54.00 4.00 (IN 13 CH40C=NOC(O)N(CH;)4 103-104 58.29 5.30 58.41 4.04

CN 14 cH.o--o=Noo o NHoH. 182 18.02 10.02

C .1 E 15 NCC=NOC(O)N(CH;)1 0110-102 22.21 22.00

Elemental analyses, percent Calculated 4 Found Compound M.P., 0. o n N o n N Example i I 16 O N-C-C=NOC(O)N(GH;)2 106-108 22.04 21.30

CHaO

(1N 17 C=NOC(O)N(CH 96.5-97.5 17.00 17. 32

I (IN is ol--o=Noo(o)N cna)z 90. 5411.5 14.69 14. 60

(IN 19 C=NO C (O)N(CH): 149. 5-154-5 14. 69 14. 31

Following are additional examples of compounds which fall within the scope of the invention, and which are prepared substantially in accordance with the method set forth hereinabove.

2,4,5 trichlorophenoxyphenylglyoxylonitrile oximino dimethylcarbamate, phenylglyoxylonitrile oximino N,N-dibutylcarbamate, p-chlorophenylglyoxylonitrile oximino N,N diethylthiocarbamate, rn-nitrophenylglyoxylonitrile oximino dimethylcarbamate, p-nitro-m-methylphenylglyoxylonitrile oximino dimethylcarbamate, p-cyanophenylglyoxylonitrile oximino dipropylthiocarbamate, and 4-cyano-3,S-dichlorophenylglyoxylonitrile oximino dimethylcarbamate.

o-Propoxyphenylglyoxylonitrile oximino diethylcarbamate, p-butoxyphenylglyoxylonitrile oximino diethylcarbamate, m-methyl and p-methylthiophenylglyoxylonitrile oximino dimethylthiocarbamate, p-propylthiophenylglyoxylonitrile oxirnino diethylcarbamate, p-butylthiophenylglyoxylonitrile oximino dibutylthiocarbamate, p-methylphenylglyoxylonitrile oximino diethylthiocarbamate, 2,4-dimethylphenylglyoxylonitrile oximino allylcarbamate, 2,4,S-trimethylphenylglyoxylonitrile oximino dimethylcarbamate, p-propylphenylglyoxylonitrile oxirnino dibutylcarbamate, and p-hexylphenylglyoxylonitrile oximino diethylcarbamate.

p-Carbomethoxyphenylglyoxylonitrile oximino diethylthiocarbamate, m-carbethoxyphenylglyoxylonitrile oximino dimethylcarbamate, p-carbopropoxyphenylglyoxylonitrile oximino dimethylcarbamate, p-carbobutoxyphenylglyoxylonitrile oximino dipropylthiocarbamate, 4- (dimethylamino) 3,5-dinitro phenylglyoxylonitrile oximino dimethylcarbamate, 3-furylglyoxylonitrile oximino diethylcarbamate, 4-tolylsulfurylphenylglyoxylonitrile oximino dimethylcarbamate, benzothienylglyoxylonitrile oximino dimethylcarbamate, p-phenylphenylglyoxylonitrile oximino diethylcarbamate, 2',4,6'-trichlorophenylphenylglyoxylonitrile oximino dimethylcarbamate, p-benzoylphenylglyoxylonitrile oximino dimethylcarbamate, 2',4',6'-trichlorobenzoylphenylglyoxyonitrile oximino dimethylcarbamate, p-fluorophenylglyoxylonitrile oximino dioctylcarbamate, p-fluorophenylglyoxylonitrile oximino diethenylcarbamate, pnitrophenylglyoxylonitrile dioctenylcarbamate, 2,4-dichlorophenylglyoxyloniuile dicyclohexylcarbamate, p-chlorophenylglyoxylonitrile diphenylcarbamate, and o-bromophenylglyoxylonitrile bis(p-chlorophenyl)carbamate, 1- naphthylglyoxylonitrile oximino dimethylcarbamate, 3-indolylglyoxylonitrile oximino dimethylcarbamate, 4-indanylglyoxylonitrile oximino dimethylcarbamate, Z-pyridylglyoxylonitrile oximino dimethylcarbamate, 5,6,7,8tetrahydro-1-naphthylglyoxylonitrile oximino dimethylcarbamate, 5-quinolylglyoxylonitrile oximino dimethylcarbamate, Z-thienylglyoxylonitrile oximino dimethylcarbamate, 4-benzofuranylglyoxylonitrile oximino dimethylcarbamate.

The following compounds will illustrate the utility of the compounds of the invention. It isto be understood that they are for the purpose of illustration only.

HERBICIDE TESTS Preand post-emergence herbicide tests method of propagating test species CrabgrassDigitaria sanguinalis Yellow foxtail grass-Setaria glauca Johnson grassSorgum halepense Barnyard grassEchin0chloa crus-galli Amaranth pigweed--Amamnthus retroflexus TurnipBrassica sp.

CottonG0ssypium hirsutum var. DPL smooth leaf Corn-Zea Mays Bean-Phase0lus vulgaris var. Black Valentine All crop and weed species were planted individually in 3" plastic pots containing potting soil. Four seeds each of corn, cotton, and snapbeans were seeded to a depth equal to the diameter of the seed. All other species were surface seeded and sprinkled with screened soil in an amount sufficient to cover the seed. Immediately after planting, all pots were watered by sub-irrigation in greenhouse trays. Pots for the pie-emergence phase were seeded one day before treatment.

Planting dates for the post-emergence phase were varied so that all seedlings would reach the desired stage of development simultaneously. The proper stage of seedling development for treatment in the post-emergence phase is as follows:

Grasses: 2 in height.

Pigweed and turnips: 1 or 2 true leaves visible above cotyledons.

Cotton: first true leaf 1" in length; expanded cotyledons.

Corn: 3"4" in height.

Beans: primary leaves expanded, growing point at primary leaf node.

Method of treatment Compounds were tested at a rate of application equivalent to 8 lbs. actual compound/ acre in a spray volume of 38 gaL/acre. Spray hood constants required to deliver the above volume are as follows:

Belt speed: 2 m.p.h.

Air pressure: adjusted to provide 38 'g.p.a. delivery.

Nozzle tip: to provide uniform cross-section flat spray.

Formulations for spray applications were prepared in 50 ml. volumes with the following three components:

(1) 1.24 grams compound (8 lb./ acre rate) (2) 49 ml. acetone or acetone-water combination. (3) 1 ml. of Tween 20.

Spray applications were made in a hood containing a movable belt and fixed spray nozzle. For passage through the spray hood, one pot of each species (pro-emergence phase) was placed on the forward half of a wooden flat Method of recording results Two weeks after treatment, preand post-emergence injury or control was visually rated, and the results were as shown in the following tables.

C omp ound OON Pre-emergenee activity, percent klll at 8 lb./A.

CG YF JG BG PW TP CT CN BN ON C=NOC(O)N(CHQ2 so so so 90 so 0 0 0 (IN OH3OC=NOC(O)N(CH3)2 10 40 40 o o o a I Cl-C=NOC(O)N(CH;) 9o 90 so 90 so 50 0 (3N C=NOC(O)N(CH3)2 100 90 100 90 0 o 0 (IN oH3-o=Noo o N oHm so 4o o o I (IJN CN=OO(O)N(CH;)2 90 90 90 o o 0 1 1N C=NOC(O)N(CH 100 90 90 7o 40 0 0 I (IJN OH:C=NOO(O)N(CH3)2 90 10o so 100 50 0 o 0 I GIN c1-o=Noo 0 N oHm 9o 60 so 90 so 0 0 Pre-emergence activity, percent kill at 8 lb./A.

Compound CG YF JG BG PW 'IP C'I CN EN (EN 01- C=NOC(O)N(CH )Z 70 60 50 90 90 90 40 30 wherein R and R are selected from the group consisting of C alkyl.

2. The carbamate having the formula No references cited. 20

ALEX MAZEL, Primary Examiner J. TOVAR, Assistant Examiner 25 US. Cl. X.R.

2 2 3 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,575,97 Dated April 20, 97

Inventor) Harold A. Kaufman It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 1, line IT, "submitted" should read --substituted--.

Column 2, line #5, posses" should read --possess--.

Column line 2, "is" should read '--it-.

Column 6, line 6, after "18.99" insert Column 6, line 7, after "3.80" insert Column lO,for the tenth compound from the top of the table, u1

BN", "0" should read Column 12, for the tenth compound from the top of the table,

under "EN", "30" should read --50--.

Column 12, for the fourteenth compound from the top of the table, under "BN", 5O" should read -80--.

Signed and sealed this 21st day of September 1971.

(SEAL) Attest:

EDWARD.M'FLETCHER ROBERT GO'ITSCIIALK Attestlng Officer Acting Commissioner of Patents 

